CN111171504A

CN111171504A - High-flame-retardancy color master batch and preparation method thereof

Info

Publication number: CN111171504A
Application number: CN202010062380.7A
Authority: CN
Inventors: 蒋接
Original assignee: Xiamen Guanyan Plastic Technology Co Ltd
Current assignee: Xiamen Guanyan Plastic Technology Co Ltd
Priority date: 2020-01-19
Filing date: 2020-01-19
Publication date: 2020-05-19

Abstract

The invention discloses a high-flame-retardancy color master batch and a preparation method thereof, and relates to the field of plastic products. The technical key points are as follows: the high-flame-retardancy color master batch comprises the following raw materials in parts by weight: 30-75 parts of ABS; 0.01-70 parts of toner; 2-20 parts of a dispersing agent; 5-30 parts of flame-retardant particles; the flame-retardant particles comprise paraffin with a first inner cavity and a second inner cavity and a clay layer wrapped outside the paraffin, sodium nitrite and powdery vermiculite are arranged in the first inner cavity, ammonium chloride is arranged in the second inner cavity, and the flame-retardant particles have the synergistic effect in the aspects of non-combustible gas asphyxiation and heat absorption, so that the flame-retardant effect is achieved, and the ammonium chloride and the sodium nitrite are acted on the advantage of the actual production of the color master batch.

Description

High-flame-retardancy color master batch and preparation method thereof

Technical Field

The invention relates to the field of plastic products, in particular to a high-flame-retardancy color master batch and a preparation method thereof.

Background

The color master batch is a novel special coloring agent for high polymer materials with the particle size of 0.1-5 mm. The color master batch is mainly used on plastics, consists of three basic elements of pigment or dye, carrier and additive, and is an aggregate prepared by uniformly loading an excessive amount of pigment into resin, so that its tinting strength is higher than that of the pigment itself. During processing, a small amount of color master batch is mixed with uncolored resin, and colored resin or products with designed pigment concentration can be obtained.

Because of the increasing demand of plastics or resin products, manufacturers have increased demand for raw materials (color masterbatch), and flame retardant property is one of the requirements. Manufacturers invent different flame-retardant color master batches in order to improve the flame retardance of the color master batches.

For example, the Chinese patent with an authorization publication number of CN103724990B discloses a color master batch for flame-retardant UV-resistant nylon, which comprises the following components: reversible thermochromic microcapsules, polyamide resin, a composite stabilizer, a flame retardant and a dispersing agent; the composite stabilizer at least comprises two of hindered phenol antioxidant, phosphite antioxidant, copper halide stabilizer, hindered amine light stabilizer, hydrolysis resistant agent, benzophenone and benzotriazole ultraviolet absorbent.

For example, the patent of Chinese invention with the publication number of CN102746559B discloses an acid-resistant anti-aging flame-retardant color master batch with excellent performance and a preparation method thereof. The color master batch is prepared by processing a polyethylene carrier, inorganic or organic toner, a stabilizer NOR and a dispersant.

Further, as disclosed in chinese patent publication No. CN106280301A, a flame retardant color masterbatch is disclosed, which comprises the following components in parts by weight: 40-60 parts of PBT resin, 10-15 parts of cold-resistant toughening agent, 3-5 parts of stabilizing agent, 5-10 parts of dispersing agent, 20-30 parts of flame retardant, 5-10 parts of antibacterial agent, 10-20 parts of toner, 5-8 parts of dispersing powder, 1-3 parts of freshener, 1-2 parts of tea tree oil and 2-5 parts of anti-blocking agent.

The prior art is similar to the flame-retardant color master batch, the flame retardant performance of the color master batch is basically improved by adding a flame retardant, and the flame retardant is mostly achieved by the heat absorption effect of the flame retardant or the high melting point property of the flame retardant, so that the problem that how to improve the flame retardant effect from other aspects of the flame retardant needs to be solved urgently is solved.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the high-flame-retardance color master batch which has the advantage of simultaneously realizing synergistic interaction from the aspect of non-combustible gas suffocation and the aspect of heat absorption so as to play a flame-retardant role.

The second purpose of the invention is to provide a preparation method of the high-flame-retardancy color master batch, which has the advantage that ammonium chloride and sodium nitrite are acted on the actual production of the color master batch.

In order to achieve the first purpose, the invention provides the following technical scheme:

the high-flame-retardancy color master batch comprises the following raw materials in parts by weight:

the flame-retardant particles comprise paraffin with a first inner cavity and a second inner cavity and a clay layer wrapped outside the paraffin, sodium nitrite and powdery vermiculite are arranged in the first inner cavity, and ammonium chloride is arranged in the second inner cavity.

Through adopting above-mentioned technical scheme, fire-retardant granule in the masterbatch finished product can play fire-retardant effect in the masterbatch, and the reason is: at normal temperature, the paraffin is solid, the solid paraffin can fix the sodium nitrite and the powdery vermiculite in the first inner cavity, and the ammonium chloride in the second inner cavity. At high temperature (generally above 80 ℃), paraffin is gradually melted, and the melted paraffin is in a fluid state, and at this time, because the fluid paraffin cannot fix sodium nitrite, powdered vermiculite and ammonium chloride, the ammonium chloride and the sodium nitrite are in contact.

The ammonium chloride and the sodium nitrite which are contacted with each other can generate N through chemical reaction at the temperature of about 85 DEG C₂，N₂Can disperse the oxygen around the ignition point, reduce the oxygen concentration near the ignition point and play a role in flame retardance in the aspect of non-gas suffocation. Meanwhile, water is generated after the ammonium chloride reacts with the sodium nitrite, and the water absorbs heat near the ignition point and evaporates, so that the fire is restrained from the aspect of heat absorption. Furthermore, the generated water can form water vapor and then can play a role in flame retardance in the aspect of non-combustible gas suffocation. Thus, the flame-retardant particles can be synergistic in terms of suffocation of non-combustible gases and in terms of heat absorptionSynergized, thereby playing a role in flame retardance.

Meanwhile, during the production of the color master batch, the color master batch is produced in an extruding mode of an extruder, and the central temperature of the extruder is generally over 200 ℃, so if the surface of paraffin is not subjected to heat insulation protection, the paraffin is directly melted, ammonium chloride and sodium nitrite are reacted in the extruder, and the flame retardant property is lost. Consequently the clay layer that sets up in this scheme can play thermal-insulated effect this moment, keeps apart the heat in the extruder, and because the thickness of clay layer is thinner, and it is relatively poor to insulate against heat, inside consequently the heat in the extruder still can partially transmit to the clay layer for the inside temperature of clay layer risees to below the softening point of paraffin.

As the temperature increases, the powdered vermiculite in the first cavity will continue to expand, causing the paraffin to expand. And the clay layer can have two conditions after being expanded and extruded by paraffin.

The first is that the clay layer is subjected to swelling crack, although the outer wall of the paraffin is directly contacted with external high temperature to be melted, the inner part of the paraffin is not completely melted at the moment, so that the ammonium chloride and the sodium nitrite are not directly contacted to be consumed, and the color master batch at the moment is extruded to an outlet of the extruder, so that the melted part of the outer wall of the paraffin can be rapidly cooled and solidified along with the color master batch, and the condition that the ammonium chloride and the sodium nitrite are reacted can not be caused. When encountering open fire, the clay layer is cracked, so that high temperature can be quickly conducted to the paraffin from the crack of the clay layer, gas generated by the reaction of ammonium chloride and sodium nitrite can be discharged from the crack of the clay layer and is sprayed out of the surface of the fluid color master batch to extinguish flame, and the color master batch still has higher flame retardant property.

The second condition is that the extrusion force of paraffin is not enough, and the clay layer does not take place to rise and split, also can not cause the condition that ammonium chloride and sodium nitrite were reacted to fall to take place this moment, consequently when the masterbatch meets naked light, along with the continuous rising of masterbatch temperature, the inflation that likepowder vermiculite in first inner chamber can last, finally makes the clay layer by rising and splitting completely, and N is cracked₂With water vapor canAnd the mixture is discharged from the swelling position of the clay layer and is sprayed out from the surface of the fluid color master batch to extinguish flame, so that the color master batch still has higher flame retardant property.

Finally, it has been found through testing that the masterbatch retains high flame retardant properties after being added as a pigment component to a plastic feedstock and extruded at high temperatures (> 200 ℃). The principle is inferred to be: the clay layer on the outer surface of the flame-retardant particle is not broken or only a small part of the clay layer is broken during the preparation of the color master batch, so that when the color master batch is used as a pigment and added into a plastic raw material and extruded at a high temperature (generally, the extrusion temperature is 220-240 ℃), the temperature is still lower when the temperature in an extruder is transferred into paraffin, the paraffin cannot be completely melted, the ammonium chloride and the sodium nitrite are not reacted, and the prepared plastic product still has high flame retardant performance at the high temperature.

In summary, when exposed fire occurs, the sodium nitrite and ammonium chloride in the color master batch react to generate N₂With the vapor, not only from the aspect of the non-combustible gas asphyxiation effect to play the flame retardant efficiency, but also can from the aspect of the heat absorption to play the flame retardant efficiency, and the flame retardant efficiency is good. Through set up clay layer at fire-retardant granule surface in the masterbatch, clay layer can get up the protection to inside paraffin of fire-retardant granule, sodium nitrite and ammonium chloride for sodium nitrate and ammonium chloride can act on in masterbatch and plastic products.

More preferably, the melting point of the paraffin is 68-73 ℃.

By adopting the technical scheme, the temperature of 68-73 ℃ belongs to the highest melting temperature of paraffin, and at the temperature, the paraffin can be ensured not to be completely melted in the extruder, so that sodium nitrite and ammonium chloride are protected, and the stability of the flame-retardant particles is improved. Meanwhile, when exposed fire occurs, the temperature of the exposed fire is far higher than the melting point of paraffin, so that the paraffin can be completely melted, and N is generated by sodium nitrite and ammonium chloride₂And the flame retardant has flame retardant effect with water vapor, and the flame retardant stability is improved.

More preferably, the clay layer is made of a material selected from the group consisting of kaolin, montmorillonite and illite.

Through adopting above-mentioned technical scheme, kaolin, montmorillonite, illite all belong to the clay, and the stickness is stronger, and solidification shaping ability is also stronger after the drying, can improve the inside stability of fire-retardant granule.

More preferably, the thickness of the clay layer is 0.2-0.3 mm.

Through adopting above-mentioned technical scheme, when the thickness of clay layer is 0.2 ~ 0.3mm, the clay layer can not be too thick, therefore the heat-proof quality of clay layer can make the heat in the extruder partly get into the clay in-situ and arouse likepowder vermiculite inflation, also can rise the crack with the clay layer after likepowder vermiculite inflation, when meetting open fire, high temperature can be normal from the clay layer in rising the position conduction of breaking to paraffin for ammonium chloride and sodium nitrite gas production, improve the production stability of fire-retardant granule and masterbatch.

Meanwhile, the clay layer cannot be too thin, so that the ammonium chloride and the sodium nitrite are prevented from being reacted in the extruder, and the production stability of the flame-retardant particles and the color master batches is improved.

More preferably, the particle size of the flame-retardant particles is 0.8-1.2 mm.

By adopting the technical scheme, the particle size of the flame-retardant particles is about one fifth of that of the color master batch, and the dispersibility of the flame-retardant particles in the color master batch is improved.

In order to achieve the second purpose, the invention provides the following technical scheme:

a preparation method of a high-flame-retardancy color master batch comprises the following steps:

step one, preparing flame-retardant particles:

i: injecting sodium nitrite and powdery vermiculite into paraffin through an injection needle, and forming a first inner cavity in the paraffin;

II: injecting ammonium chloride into the paraffin through an injection needle, and forming a second inner cavity in the paraffin;

III: after the injection needle is pulled out, the periphery of the pinhole opening of the paraffin is extruded by external force to seal the pinhole opening of the paraffin, and then internal particles are obtained;

IV: soaking the internal particles in clay and water slurry for 5-10 s, taking out the internal particles, and drying at the temperature of 45-55 ℃ to obtain flame-retardant particles;

and step two, uniformly mixing the ABS, the toner, the dispersing agent and the flame-retardant particles in parts by weight, then putting the mixture into a double-screw extruder with the internal temperature of 200-220 ℃ for extrusion, cooling, solidification and grain cutting to obtain the high-flame-retardancy color master batch.

By adopting the technical scheme, in the first step, after the sodium nitrite, the powdery vermiculite and the ammonium chloride are injected into the paraffin through the injection needle, the sodium nitrite, the powdery vermiculite and the ammonium chloride can be stacked in the paraffin to form the first inner cavity and the second inner cavity. Because the syringe needle can form the pinhole in paraffin after extracting, and the paraffin texture is softer, consequently can make paraffin warp and then make the opening of pinhole seal through external force extrusion. Then, the inner particles are immersed in the slurry, the clay is hung on the outer wall of the inner particles, and the clay is solidified on the surface of the paraffin wax along with drying to play a skeleton and protection role.

And then, after the raw materials of the color master batch pass through a double-screw extruder, the flame-retardant particles can be dispersed in the color master batch to play a flame-retardant role.

Preferably, in the step IV, before the inner particles are immersed in the slurry, aerogel powder is added to the slurry, and the weight ratio of aerogel to clay is 50 to 80: 1, stirring uniformly.

By adopting the technical scheme, the aerogel powder can play a certain heat insulation effect, so that paraffin cannot be completely dissolved in the extruder, and the stability of the flame-retardant particles is improved.

In summary, compared with the prior art, the invention has the following beneficial effects:

(1) flame-retardant particles are added into the raw materials of the color master batch, and the flame-retardant particles generate gas through the reaction of sodium nitrite and ammonium chloride in the flame-retardant particles, so that the gas asphyxiation effect is realized, and the flame-retardant property is good; through the powdery vermiculite in the flame-retardant particles and the clay layer outside the flame-retardant particles, the sodium nitrite and the ammonium chloride can be acted on the production of the color master batch.

(2) Through adding the aerogel in clay layer when preparing the outer clay layer of fire-retardant granule, the aerogel can improve the heat-proof quality on clay layer as required, makes fire-retardant granule can withstand the high temperature of extruder central temperature, guarantees fire-retardant granule's validity.

Drawings

FIG. 1 is a cross-sectional view of a flame retardant pellet of the first embodiment.

Reference numerals: 1. a first lumen; 2. a second lumen; 3. paraffin wax; 4. sodium nitrite; 5. powdered vermiculite; 6. ammonium chloride; 7. an inner particle; 8. and (6) an adhesive layer.

Detailed Description

The invention is described in detail below with reference to the figures and examples.

Example 1: referring to fig. 1, the raw materials of the high flame retardant color master batch and the corresponding parts by weight thereof are shown in table 1. The flame-retardant particles comprise paraffin 3 provided with a first inner cavity 1 and a second inner cavity 2 and a clay layer 8 wrapped on the outer side of the paraffin 3, sodium nitrite 4 and powdery vermiculite 5 are arranged in the first inner cavity 1, and ammonium chloride 6 is arranged in the second inner cavity 2.

The high-flame-retardancy color master batch is prepared by the following steps:

step one, preparing flame-retardant particles:

i: powdery sodium nitrite 4 and powdery vermiculite 5 (with the grain diameter of 0.1-0.2 mm) are injected into No. 62 paraffin 3 through an injection needle with the model of 20G, and a first inner cavity 1 is formed in the paraffin 3 at the moment. Wherein the weight ratio of the sodium nitrite 4 to the powdery vermiculite 5 is 2:1, and the volume of the first inner cavity 1 is 1/5 of the volume of the paraffin 3;

II: the second cavity 2 is formed in the paraffin 3 by injecting powdered ammonium chloride 6 into the paraffin 3 through a 20G injection needle. Wherein the weight ratio of the ammonium chloride 6 to the sodium nitrite 4 is 1:1, and the second inner cavity 2 is not communicated with the first inner cavity 1.

III: after the injection needle is pulled out, the periphery of the pinhole opening of the paraffin 3 is extruded by an external force (forceps in the embodiment) to seal the pinhole opening of the paraffin 3, and then internal particles 7 are obtained;

IV: the inner particles 7 were taken out by dipping the inner particles 7 in a slurry of clay and water for 5 seconds by tweezers. The inner particles 7 were dried at a temperature of 50 ℃ to obtain flame retardant particles. Wherein the clay in the step is kaolin in Zhangzhou city, the weight ratio of the clay to the water in the slurry in the step is 6:1, the thickness of the clay layer 8 is 0.43mm through slicing and measurement of the flame-retardant particles obtained in the step, and the particle size of the flame-retardant particles obtained in the step is 1.56 mm.

And step two, uniformly mixing ABS, toner, a dispersing agent and flame-retardant particles in corresponding parts by weight in a stirrer (30r/min and 15min), then putting the mixture into a double-screw extruder with the internal temperature of 210 ℃ for extrusion, cooling and solidifying the extruded product through a water tank, and granulating the product through a granulator to obtain the high-flame-retardancy color master batch. The toner in the step can use different toners according to different color requirements, and the dispersant in the step is ethylene bis stearamide.

Examples 2 to 5: the high-flame-retardancy color master batch is different from the embodiment 1 in that the components and the corresponding parts by weight are shown in the table 1.

TABLE 1 Components and parts by weight of examples 1-5

Example 6: a high flame-retardant color master batch, which is different from example 1 in that the decomposition temperature of paraffin wax in this example is 72.1 ℃, and paraffin wax in this example is prepared according to example 2 of granted patent publication No. CN 107513417B.

Example 7: a color master batch with high flame retardance, which is different from the color master batch in example 1, wherein the clay layer is made of montmorillonite produced in north Hebei province.

Example 8: a color master batch with high flame retardance, which is different from the color master batch in the embodiment 1 in that the raw material of an clay layer in the embodiment is illite produced in Zhejiang province.

Example 9: a high flame-retardant color master batch, which is different from the color master batch in example 1 in that in step one, the weight ratio of clay to water in the slurry is 4:1, and the thickness of the clay layer is 0.26mm as measured after the flame-retardant particles obtained in this example are sliced.

Example 10: a high flame-retardant color master batch, which is different from the color master batch in example 1 in that the particle size of the flame-retardant particles is reduced by reducing the volume of paraffin so that the particle size of the flame-retardant particles in this example is 1.1 mm.

Example 11: a high flame-retardant color master batch, which is different from the color master batch in example 1 in that the particle size of the flame-retardant particles is reduced by reducing the volume of paraffin so that the particle size of the flame-retardant particles in this example is 0.8 mm.

Example 12: a high flame resistance color master batch, which is different from the color master batch of the embodiment 1 in that in the step IV of the step one, aerogel powder is added into the slurry before the inner particles are immersed into the slurry, and the weight ratio of aerogel to clay is 50: 1, stirring uniformly by a stirrer.

Example 13: a high flame retardant color master batch, which is different from the embodiment 12 in that the weight ratio of aerogel to clay is 65: 1.

example 14: the high-flame-retardancy color master batch is different from the embodiment 1 in that the weight ratio of aerogel to clay is 80: 1.

example 15: a high flame-retardant color master batch, which is different from example 1 in that the decomposition temperature of paraffin wax in this example is 72.1 ℃, and paraffin wax in this example is prepared according to example 2 of granted patent publication No. CN 107513417B.

In step IV, aerogel powder is added to the slurry before the inner particles are immersed in the slurry, the weight ratio of aerogel to clay is 50: 1, stirring uniformly by a stirrer.

In step IV, the weight ratio of clay to water in the slurry is 4:1, and the thickness of the clay layer measured after slicing the flame retardant particles obtained in this example is 0.26 mm.

This example reduced the particle size of the flame retardant particles by reducing the volume of the paraffin wax so that the particle size of the flame retardant particles was 1.1 mm.

Comparative example 1: a color masterbatch, which is different from the color masterbatch in example 1 in that, in this example, no flame retardant particles are added to the raw materials of the color masterbatch.

Comparative example 2: an acid-resistant anti-aging flame-retardant color master batch with excellent performance is prepared in example 1 of a Chinese patent with an issued patent publication number of CN 102746559B.

Test samples: the color concentrates obtained in examples 1 to 15 were used as test samples 1 to 15, and the color concentrates obtained in comparative examples 1 to 2 were used as control samples 1 to 2.

Test-flame retardancy test

The test method comprises the following steps: the test is referred to the fire-retardant rating UL94 standard.

And (3) test results: the flame retardant performance results are shown in table 2.

Test two-mechanical Performance test

The test method comprises the following steps:

and (3) testing tensile property: the tensile strength of the test samples 1-15 and the control samples 1-2 is tested according to GB1040-92 Plastic tensile Property test method. The test was repeated 10 times, discarding the maximum 2 values and the minimum 2 values of each group, and averaging the rest.

And (3) testing the bending property: the bending properties of the test samples 1 to 15 and the control sample 1 to 2 were tested with reference to GB/T9341-2008 "determination of Plastic bending Properties". The test was repeated 10 times, discarding the maximum 2 values and the minimum 2 values of each group, and averaging the rest.

And (3) test results: the mechanical properties are measured as shown in Table 2

TABLE 2 test results of flame retardancy and mechanical Properties of test samples 1-15 and control samples 1-2

And (3) data analysis:

as can be seen from the comparison of the test samples 1 to 15 with the control samples 1 to 2, the control sample 1 without the flame retardant particles is completely burned, which indicates that the control sample 1 has no flame retardant effect, and only the test samples 1 to 15 with the flame retardant particles added have the flame retardant effect. And the flame retardant grade of the comparison sample 2 is only V-2, and the lowest flame retardant grade of the test sample 1-15 is V-0, which shows that the flame retardant property of the existing partial flame-retardant color master batch is poor, and the flame retardant property of the color master batch provided by the scheme can exceed that of the existing partial flame-retardant color master batch.

Meanwhile, most of the existing flame retardants have the flame retardant effect in a heat absorption mode, and the sodium nitrite and the ammonium chloride react to generate gas to achieve the flame retardant effect, so that the flame retardant effect can be achieved in the aspect of heat absorption, the flame retardant effect can be achieved in the aspect of gas suffocation, and the flame retardant property is more excellent than that of the existing flame retardant.

It can be seen from the tensile strength and the bending strength that the differences between the test samples 1-15 and the comparison samples 1-2 are not large in the tensile strength and the bending strength, which indicates that the scheme adds the flame-retardant particles into the raw materials of the color master batch without causing adverse effects on the tensile strength and the bending strength of the color master batch, and the color master batch has stable mechanical properties.

The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.

Claims

1. The high-flame-retardancy color master batch is characterized by comprising the following raw materials in parts by weight:

30-75 parts of ABS;

0.01-70 parts of toner;

2-20 parts of a dispersing agent;

5-30 parts of flame-retardant particles;

the flame-retardant particles comprise paraffin (3) provided with a first inner cavity (1) and a second inner cavity (2) and a clay layer (8) wrapped outside the paraffin (3), sodium nitrite (4) and powdery vermiculite (5) are arranged in the first inner cavity (1), and ammonium chloride (6) is arranged in the second inner cavity (2).

2. The color masterbatch with high flame retardancy according to claim 1, wherein the melting point of the paraffin wax (3) is 68-73 ℃.

3. The masterbatch with high flame retardancy according to claim 1, wherein the clay layer (8) is made of any one of kaolin, montmorillonite and illite.

4. The masterbatch with high flame retardancy according to claim 4, wherein the clay layer (8) has a thickness of 0.2-0.3 mm.

5. The color master batch with high flame retardance according to claim 1, wherein the particle size of the flame-retardant particles is 0.8-1.2 mm.

6. The preparation method of the high-flame-retardancy color master batch is characterized by comprising the following steps of:

step one, preparing flame-retardant particles:

i: injecting sodium nitrite (4) and powdered vermiculite (5) into paraffin (3) through an injection needle, and forming a first inner cavity (1) in the paraffin (3);

II: injecting ammonium chloride (6) into the paraffin (3) through an injection needle, and forming a second inner cavity (2) in the paraffin (3);

III: after the injection needle is pulled out, the periphery of the pinhole opening of the paraffin (3) is extruded by external force to seal the pinhole opening of the paraffin (3) and obtain internal particles (7);

IV: soaking the internal particles (7) in slurry of clay and water for 5-10 s, taking out the internal particles (7), and drying at the temperature of 45-55 ℃ to obtain flame-retardant particles;

7. The preparation method of the color master batch with high flame retardance according to claim 6, wherein in the step IV, before the inner particles (7) are immersed in the slurry, aerogel powder is added into the slurry, and the weight ratio of aerogel to clay is 50-80: 1, stirring uniformly.